JP4587679B2 - Process for producing aromatic-containing cyclic olefin copolymer - Google Patents

Description

  The present invention provides an aromatic-containing cyclic olefin copolymer having excellent chemical properties such as heat resistance, heat aging resistance, optical properties such as transparency and refractive index, and mechanical properties such as impact resistance. The present invention relates to a method, a copolymer obtained by the production method, an optical material and an electric / electronic material comprising the copolymer.

Polymer materials are attracting attention as various optical materials and electrical / electronic materials because they are lighter and have better mechanical properties than glass materials. In addition, since the polymer material is excellent in moldability, it is easy to make it compact and thin, and it can be expected that the product is smaller, lighter and more durable than the glass material. In addition, it is possible to manufacture flexible optical materials that take advantage of the flexibility and toughness of polymers. With the progress of information processing technology in recent years, optical communication fibers, optical integrated circuits, wiring boards, etc. are made of polymer materials. It is expected that it can be manufactured using Performance required for materials for these applications includes optical properties such as transparency, heat resistance, impact resistance, and dielectric properties, electrical properties, and mechanical properties.
For example, conventionally, polycarbonate resins, polymethyl methacrylate resins, aromatic-containing cyclic olefin resins and the like are known as resins having excellent transparency. Polycarbonate resins are excellent in transparency, heat resistance, heat aging resistance, impact resistance, etc., but have the disadvantage that they are easily attacked by strong alkalis and inferior in chemical resistance. Moreover, polymethylmethacrylate resin has the fault that solvent resistance, heat resistance, moisture resistance, etc. are bad.

In addition, the cyclic olefin-based resin has a high glass transition temperature and excellent transparency as compared with an olefin-based resin having no ring structure. However, when compared with the above polycarbonate resin or polymethyl methacrylate resin, Excellent in chemical properties, solvent resistance, mechanical properties, etc., but inferior in heat resistance and transparency. For example, according to Patent Document 1, a cyclic olefin copolymer using ethylene and norbornene by addition polymerization is excellent in optical properties, and furthermore, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, Although it is a resin with a balanced mechanical strength, it is disclosed that it has a problem in transparency due to partial crystallization due to non-uniform composition.
Alternatively, as liquid crystal display elements used for electric and electronic materials, a thin film transistor is provided in each pixel, and an active matrix liquid crystal display element that drives each pixel by a scanning signal and a data signal has a high display quality, and will become the mainstream in the future. Things are expected. In this type of liquid crystal display element, an active matrix substrate in which a thin film transistor array is formed on a transparent insulating substrate and a counter substrate in which a transparent electrode is formed on the transparent insulating substrate are arranged opposite to each other, and a liquid crystal material is sealed in the gap. it can.
Therefore, the transparent insulating substrate constituting the active matrix substrate is required to have high heat resistance for the formation of an insulating film, etc., and the plastic substrate, which is inferior in heat resistance compared to glass, is deformed during processing and is difficult to use. It was.

  On the other hand, a polymer obtained by ring-opening metathesis polymerization of a cyclic olefin is excellent in transparency, but has a problem that heat resistance is difficult to control and a polymer having high heat resistance cannot be obtained. In addition, since the polymer obtained by ring-opening metathesis polymerization contains a double bond in the main chain, a hydrogenation step is necessary from the viewpoint of thermal stability. It is disadvantageous.

  Patent Document 2 discloses a random copolymer obtained by copolymerizing a raw material containing ethylene and a 5-aryl-bicyclo [2,2,1] hept-2-ene compound (phenyl-norbornene). Yes. This copolymer is produced using a catalyst composed of a soluble vanadium compound and an organoaluminum compound, and the glass transition point of a product containing 29 mol% of phenyl-norbornene has been shown to be as high as 150 ° C. . Further, phenyl-norbornene, which is a raw material, can be easily produced by a Diels-Alder reaction between an aromatic olefin compound (for example, styrene, α-methylstyrene, indene, etc.) and cyclopentadiene or dicyclopentadiene. It has been shown.

  Furthermore, according to Patent Document 3 and Patent Document 4, it is disclosed that the obtained aromatic-containing cyclic olefin copolymer has high impact resistance. However, for example, in Patent Document 3, when a metallocene / MAO (or B-type cocatalyst) -based catalyst is used, even if the copolymerization of an α-olefin and an aromatic-substituted norbornene is carried out, the copolymerizability is poor and the polymerization is performed. There was a limit in obtaining a copolymer having low activity, for example, having a high glass transition point.

In addition, these aromatic-containing cyclic olefin copolymers have poor heat aging resistance compared to cyclic olefin copolymers not containing aromatics such as norbornene and tetracyclododecene, and even under relatively low temperature conditions. It easily oxidizes, yellows, and undergoes crosslinking and decomposition reactions. Therefore, the molding processability is poor, and depending on the use conditions, the optical properties of the resulting copolymer are lowered, making it difficult to use in the same application, and further improvements in properties are desired.
Japanese Patent No. 1988424 Japanese Patent No. 2029392 Japanese National Patent Publication No. 11-504669 Japanese Patent No. 3203029

  The object of the present invention is to solve the problems of the conventional aromatic-containing cyclic olefin copolymer as described above, and to be excellent in optical material properties such as heat resistance, impact resistance, heat aging resistance and transparency, and Another object of the present invention is to provide a method for producing an aromatic-containing cyclic olefin copolymer having a high glass transition point, a copolymer produced thereby, an optical material containing the copolymer, and an electric / electronic material.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have developed a catalyst in which an α-olefin and an aromatic-containing cyclic olefin having a specific structure are combined with a metallocene compound having a specific structure and an aluminoxane. The inventors have found that the above-described object can be achieved by copolymerization in the presence of the present invention, and have reached the present invention.

That is, the aromatic-containing cyclic olefin having a specific structure in the present invention is an aromatic composed of 5-methyl or ethyl-5-phenyl-bicyclo [2,2,1] hept-2-ene (methyl or ethylphenylnorbornene). containing a cyclic olefin, and α- olefin, by copolymerization in the presence of a catalyst obtained by combining the metallocene compound having a specific structure and methyl aluminoxane, the resulting copolymer is excellent in heat resistance, heat aging resistance, And optical properties such as transparency were found to be extremely excellent. Therefore, the obtained aromatic-containing cyclic olefin copolymer resin is extremely useful as an optical material such as an optical fiber, a lens, a disk, or a window glass, or an electric / electronic material.

(1) An α-olefin and an aromatic-containing cyclic olefin composed of 5-methyl or ethyl-5-phenyl-bicyclo [2,2,1] hept-2-ene (methyl or ethylphenylnorbornene) are mixed with methylene ( A process for producing an aromatic-containing cyclic olefin copolymer, comprising copolymerizing in the presence of a catalyst comprising cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride and methylaluminoxane.
(2) said and α- olefin, and the aromatic-containing cycloolefin, further, bicyclo [2,2,1] hept-2-on en the 81 and cycloolefin consisting (norbornene) Ru is copolymerized) The manufacturing method of aromatic-containing cyclic olefin copolymer of description.
( 3 ) Obtained by the production method described in (1) or (2 ) above, and a differential scanning calorimeter (temperature rising from 30 ° C. to 350 ° C. in air (air supply rate 50 ml / min) 5 ° C. An aromatic-containing cyclic olefin copolymer having an exothermic starting temperature of 180 ° C. or higher as measured by raising the temperature at / min.
(4) including optical science material an aromatic-containing cycloolefin copolymer according to (3).
(5) the including electrical and electronic materials an aromatic-containing cycloolefin copolymer according to (3).

The method for producing an aromatic-containing cyclic olefin copolymer of the present invention is an efficient production method in which the catalyst has high activity and high copolymerizability, and the obtained aromatic-containing cyclic olefin copolymer. Has an extremely high glass transition point, and is excellent in chemical properties such as heat resistance, heat aging resistance, low yellowness, optical properties such as transparency and refractive index, and mechanical properties such as impact resistance. .
In particular, the aromatic-containing cyclic olefin copolymer of the present invention is excellent in heat aging resistance as well as heat resistance. Although conventional aromatic-containing cyclic olefin copolymers have high heat resistance, they require high molding processing temperature due to their poor heat aging resistance, so that deterioration occurs during molding processing, and even when they are used as materials. Deterioration due to use under high temperature conditions is unavoidable, and optical characteristics have been degraded due to deterioration. However, since the copolymer of the present invention has high heat aging resistance without impairing heat resistance, it can suppress deterioration during molding and the like, and has excellent transparency, low yellowness optical materials, and electric / electronic materials. provide.

  Hereinafter, the present invention will be specifically described. As the α-olefin (monomer component [A]) used in the present invention, in addition to ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, A linear α-olefin having 1 to 20 carbon atoms such as 1-dodecene and 1-tetradecene is preferable. Of these, ethylene is particularly preferable.

In the present invention, the aromatic component-containing cyclic olefin which is the monomer component [B] to be copolymerized with the monomer component [A] is 5-methyl-5-phenyl-bicyclo [2,2,1] hept-2-. Ene (methylphenylnorbornene) or 5-ethyl-5-phenyl-bicyclo [2,2,1] hept-2-ene (ethylphenylnorbornene) .

  The monomer component [B] can be obtained by reacting a corresponding cyclopentadiene and an aromatic-containing olefin with a Diels-Alder reaction. For example, a method for producing 5-methyl-5-phenyl-bicyclo [2,2,1] hept-2-ene includes dicyclopentadiene which is a dimer of cyclopentadiene in an autoclave which has been thoroughly dried and substituted with nitrogen. And α-methylstyrene is added in a 2.2-fold molar amount with respect to dicyclopentadiene. As a polymerization inhibitor, 1.0% by weight of tert-butylcatechol is added to α-methylstyrene. Slightly pressurize with nitrogen and heat up to 180 ° C. The reaction is carried out for 3 to 9 hours after the internal temperature reaches 180 ° C. After the scheduled reaction time has elapsed, the reaction solution is cooled to room temperature and the reaction solution is taken out. The reaction solution is washed with an aqueous solution of potassium hydroxide to remove the polymerization inhibitor. Thereafter, calcium hydride is added as a dehydrating agent, and the desired aromatic-containing cyclic olefin can be obtained by distillation under reduced pressure.

  In the present invention, in the copolymer obtained by copolymerizing the monomer component [A] and the monomer component [B], the monomer component [B] is contained at least 5 mol% or more. The repeating unit of the monomer component [A] is 20 to 95 mol%, preferably 30 to 90 mol%, particularly preferably 40 to 90 mol%, based on the entire copolymer. On the other hand, the repeating unit of the monomer component [B] is 80 to 5 mol%, preferably 70 to 10 mol%, particularly 60 to 10 mol% of the entire copolymer. In the copolymer containing the monomer component [C], the repeating unit of the monomer component [C] is 70 mol% or less, preferably 60 mol% or less, particularly preferably 50 mol% or less in the copolymer. . Further, the monomer component [A], monomer component [B], and monomer component [C] contained in the copolymer are not limited to one type, and a plurality of types may be mixed and used.

In the present invention, when the above monomer components [A], [B] and [C] are copolymerized to produce an aromatic-containing cyclic olefin copolymer, methylene (cyclopentadienyl) (tetramethylcyclopenta). dienyl) zirconium dichloride (hereinafter also referred to as the metallocene compound [a]) and methyl aluminoxane (hereinafter, also referred to as aluminoxanes [b]), and an organoaluminum compound as needed [c] and Ru is used a catalyst comprising a.

Further, the metallocene compound with [a], another component der Ru methyl Aruminokisa emission constituting the catalyst used in the present invention (MAO) preferably have a molecular weight from 200 to 10,000.
The methyl aluminoxanes fang aromatic hydrocarbon solvents (benzene, toluene, etc.), but soluble in an, in the present invention, out of such methyl aluminoxane, an aluminoxane and insoluble in aromatic hydrocarbon solvents Can be used.

  The aluminoxane is a known method, for example, a method in which a trialkylaluminum compound is dissolved in a hydrocarbon solvent, and an equivalent amount of water is gradually added to the trialkylaluminum compound to hydrolyze or a copper sulfate solution in a hydrocarbon solvent. It can be produced by a method in which a hydrate or the like is suspended and hydrolyzed by bringing 1 to 3 equivalents of a trialkylaluminum compound into contact with the hydrated crystal water. The aluminoxane insoluble in the aromatic hydrocarbon solvent is, for example, a method in which an aluminoxane solution is brought into contact with water or an active hydrogen-containing compound, or a method in which an organoaluminum compound such as trialkylaluminum is brought into contact with water. Can be manufactured. The aluminoxane used may be synthesized as described above, but of course commercially available products can also be used.

  The catalyst used in the present invention can further contain an organoaluminum compound [c] as a catalyst component, if necessary. Examples of the organoaluminum compound [c] include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-iso-butylaluminum, dimethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum phenoxide and the like. Of these, trimethylaluminum, triethylaluminum, and tri-iso-butylaluminum are particularly preferable.

The amount of the catalyst components [a] to [c] used is preferably 10 ⁻⁶ to 1 gram atom / liter, particularly preferably 10 ⁻ as the transition metal concentration of the metallocene compound [a] in the polymerization system. ⁵ to 10 ^-1 gram atoms / liter. The amount of aluminoxane [b] used is preferably 10 ⁻⁴ to 10 gram atoms / liter, particularly preferably 10 ⁻³ to 1 gram atoms / liter, as the aluminum concentration in the polymerization system. In addition, the amount of the organoaluminum compound [c] used as necessary is preferably 10 ⁻⁶ to 10 gram atoms / liter, in particular, as an aluminum concentration in the polymerization system, apart from the aluminoxane [b]]. Preferably, it is 10 ⁻⁵ to 1 gram atom / liter.

  In the present invention, each of the above catalyst components may be supplied to the polymerization system as a premixed solution in an appropriate solvent such as an aromatic hydrocarbon solvent such as toluene, or each of the above components may be added to a monomer or an appropriate solvent. The dissolved solutions may be fed simultaneously or separately into the polymerization system and mixed there. Especially, it is preferable to mix the said metallocene compound (a), aluminoxane (b), and the organoaluminum compound (c) as needed, and to supply it to a polymerization system.

  In the present invention, the polymerization method for copolymerizing the monomer component [A], the monomer component [B], and, if necessary, the monomer component [C] using the catalyst is a batch type or continuous type gas phase polymerization. Any polymerization method such as a method, a bulk polymerization method, a solution polymerization method using an appropriate solvent, or a slurry polymerization method may be used. Among them, since the reaction system is uniform, heat conduction is good, control of the polymerization reaction is easy, and the polymerization product is uniformly dispersed in the solvent and does not deposit around the active point. The solution polymerization method is preferred because it is difficult to occur and bulky monomers are easily polymerized. As the solvent used in the solution polymerization method, an inert hydrocarbon solvent is preferably used, but the monomer component [B] or the monomer component [C] may be used as a solvent. Examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, and decalin, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and dimethylcyclohexane, Aromatic hydrocarbons such as benzene, toluene and xylene, petroleum fractions such as naphtha, kerosene and light oil can be used, and these solvents may be used in combination. A preferred solvent is an aromatic hydrocarbon, and a particularly preferred solvent is toluene.

As polymerization conditions, the temperature is generally -100 to 250 ° C, preferably -50 to 200 ° C, particularly preferably 0 to 150 ° C. The pressure is generally 10 MPa or less, preferably from normal pressure to 5 MPa. The reaction time varies depending on the reaction conditions such as monomer type, catalyst concentration, polymerization temperature and the like, but is usually 3 minutes to 5 hours, preferably 5 minutes to 3 hours. In addition, this reaction time has shown the average residence time of the polymerization liquid, when making it copolymerize by a continuous type. The molecular weight of the target copolymer can be controlled by introducing hydrogen into the system.
The catalyst used in the present invention is characterized by high activity and high copolymerization of the aromatic-containing cyclic olefin as compared with conventional catalysts. By copolymerization using such a catalyst, a copolymer having a high glass transition point and excellent heat resistance can be obtained. Furthermore, in the present invention, by using a specific aromatic-containing cyclic olefin, the obtained copolymer has excellent transparency, low yellowness, and heat aging resistance, which has not been obtained conventionally.

A solution containing the target aromatic-containing cyclic olefin copolymer is obtained by the reaction conditions shown above. In this polymerization solution, the aromatic-containing cyclic olefin copolymer is usually contained in a concentration of preferably 1 to 500 g / liter, particularly preferably 5 to 300 g / liter. A cyclic olefin copolymer is obtained by treating this polymerization solution according to a conventional method. For example, after methanol is added to the polymerization solution to stop the reaction, the catalyst components are adsorbed on a filter aid such as celite, and then the cerite is filtered and separated together with the adsorbed catalyst, or silica gel is contacted with the polymerization solution. Thus, the catalyst component can be separated from the copolymer. Next, the target aromatic-containing cyclic olefin copolymer can be obtained from the polymerization solution by the following methods (A) and (B).
(A) It is put into a poor solvent such as acetone in a large excess (for example, 3 times or more) under strong stirring to precipitate a cyclic olefin copolymer. The precipitated copolymer is filtered off and washed with a poor solvent for the copolymer such as acetone. If necessary, the precipitated copolymer is redissolved in a good solvent, and again injected into a poor solvent such as acetone to precipitate a cyclic olefin copolymer. Using an evaporator or the like, unreacted monomers and solvent components are removed by evaporation, and the polymer is obtained while drying.

The aromatic-containing cyclic olefin-based copolymer obtained by the present invention is excellent in heat aging resistance as well as heat resistance, impact resistance, and transparency, and is produced in conventional aromatic-containing cyclic olefin copolymers. Oxidation reaction, decomposition reaction, and cross-linking reaction are not caused by heating. Such a copolymer of the present invention has the following three features.
a. There is no reduction in transparency or coloration due to the oxidation reaction.
b. No degradation of strength due to decomposition reaction, mixing of bubbles, bad odor during molding processing, etc.
c. The generation of gel due to the cross-linking reaction and the accompanying distortion do not occur.
From these features, it is extremely excellent as an optical material. More specifically, since a conventional aromatic-containing cyclic olefin copolymer has high heat resistance, a high molding processing temperature is required. As a result, deterioration occurs at the time of molding due to poor heat aging resistance, and even when used as a material, deterioration due to use under high temperature conditions is unavoidable, and optical characteristics are deteriorated due to deterioration, so as an optical material It was difficult to use. However, since the copolymer of the present invention can realize high heat aging resistance without impairing the original high heat resistance, it can suppress a decrease in optical properties due to a deterioration reaction and becomes an excellent optical material.

  Thus, the molecular weight of the aromatic-containing cyclic olefin polymer obtained in the present invention is generally 5,000 to 300,000 in weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). 10,000 to 200,000. The molecular weight distribution (Mw / Mn) is from 1.5 to 3.5, particularly preferably from 1.6 to 2.5. When the copolymer is used as an optical material, the total light transmittance measured with a 3 mm-thick plate-shaped molded article is 85% or more, preferably 88% or more, and particularly a conventional aromatic-containing cyclic olefin. 90% or more not obtained in the polymer can be obtained. Further, the yellowness is 2.5 or less, particularly 2.0 or less, which the conventional aromatic-containing cyclic olefin polymer does not have. The refractive index is as high as 1.5 to 1.6, and the heat generation start temperature associated with oxidative degradation, which is a measure of heat aging resistance, is 180 ° C. or higher. The glass transition temperature (Tg) is 60 to 260 ° C, particularly 80 to 240 ° C.

  Moreover, the copolymer obtained by this invention can be shape | molded by a known method similarly to a normal thermoplastic resin. For example, single screw extruder, vented extruder, twin screw extruder, conical twin screw extruder, conyder, plasticizer, mixed screwer, twin screw conical screw extruder, planetary screw extruder, geared extruder A molded body having a desired shape can be obtained by performing extrusion molding, injection molding, blow molding, rotational molding, or the like using a molding machine such as a machine or a screwless extruder.

  Anti-oxidant, heat stabilizer, weather stabilizer, light stabilizer, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, natural oil, synthetic as needed Oils, waxes, and the like can be blended, and the blending ratio can be set as appropriate.

  Moreover, the aromatic-containing cyclic olefin polymer obtained by this invention can contain an oxidation stabilizer as needed. As the oxidation stabilizer, a phenol stabilizer, a phosphorus stabilizer, a sulfur stabilizer, a fatty acid metal salt stabilizer, a fatty acid ester stabilizer, or the like can be used.

  For example, phenolic stabilizers include tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxy And phenyl) propionic acid alkyl esters and 2,2′-oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate. Examples of the fatty acid metal salt stabilizer include zinc stearate, calcium stearate, and 12-hydroxycalcium stearate. Examples of fatty acid ester stabilizers include glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate and glycerin dilaurate; pentaerythritol monostearate, pentaerythritol mono Examples include fatty esters of pentaerythritol such as laurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate.

  In the present invention, it is particularly preferable to use a combination of a phenolic stabilizer and a fatty acid ester stabilizer of a polyhydric alcohol, and the fatty acid ester stabilizer of the polyhydric alcohol is a trihydric or higher alcoholic alcohol. A polyhydric alcohol fatty acid ester in which a part of the hydroxyl group is esterified is preferable. Examples of this combination include a combination of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerol monostearate.

  When the above phenol-based stabilizer is used, it is usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the aromatic-containing cyclic olefin copolymer. Used. The fatty acid ester stabilizer of the polyhydric alcohol is usually used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the cyclic olefin copolymer.

  In addition, the aromatic-containing cyclic olefin copolymer of the present invention includes silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide as long as the object of the present invention is not impaired. , Magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, A filler such as graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, α-olefin fiber having 2 or more polycarbons, polypropylene fiber, polyester fiber, and polyamide fiber may be blended.

  Furthermore, the aromatic-containing cyclic olefin copolymer of the present invention can be used alone or in combination with other polymer compounds. There is no restriction | limiting in particular in the high molecular compound which can be mixed and used with the aromatic cyclic olefin type copolymer of this invention, A thermoplastic resin, reaction curable resin, or a rubber-like substance can be used.

  Examples of polymer compounds that can be used by mixing with the cyclic aromatic-containing olefin copolymer of the present invention are shown below. Polyolefin (eg, low density polyethylene to high density polyethylene, LLDPE, VLDPE, polyethylene such as modified polyethylene, polypropylene, poly-4-methylpentene-1, polybutene-1); polyvinyl chloride, poly Vinyl bromide, polyvinyl fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-butadiene copolymer, Vinyl chloride-acrylic acid ester copolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, polyvinylidene chloride, polytetrafluoroethylene, polytrifluorochloroethylene and polyfluoride Vinylidene chloride; polyvinyl alcohol and poly (Co) polymers of unsaturated alcohols such as ril alcohol; (co) polymers of unsaturated ethers such as polyvinyl ether and polyallyl ether; (co) polymers of unsaturated carboxylic acids such as acrylic acid and methacrylic acid Polymers; polyvinyl esters such as polyvinyl acetate; polyallyl esters such as polyphthalic acid; polyacrylic acid esters, polymethacrylic acid esters, and (co) polymers of maleic acid esters or fumaric acid esters; acrylonitrile or methacrylonitrile (Co) polymer of malononitrile or fumaronitrile; (co) polymer of polycyanide vinylidene; polystyrene, poly α-methyl styrene, poly p-methyl styrene, styrene-α-methyl styrene copolymer, styrene-p-methyl Styrene copolymer, polyvinylbenzene and poly Halogenated styrene; polyvinyl pyridine, poly N-vinyl pyrrolidine and poly N-vinyl pyrrolidone; polycarbonate; nylon 6, nylon 6,6, polyparaphenylene terephthalamide; acid anhydrides such as maleic anhydride and fumaric anhydride ) Polymers, and (co) polymers of compounds obtained by imidizing these acid anhydrides; polyamideimide, polyetherimide, polyimide, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyethersulfone and polyarylate; unsaturated polyester Resin, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin and silicon resin; polybutadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene -Propylene copolymer rubber and isoprene-isobutylene copolymer rubber; polymers having a carbazole skeleton such as polyvinyl carbazole; and celluloses such as ethyl cellulose and regenerated cellulose. These polymer compounds and the aromatic-containing cyclic olefin copolymer of the present invention can be kneaded using a normal kneading apparatus.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In Examples and Comparative Examples, the physical properties of the copolymers were measured by the following analytical methods.
(1) Content (molar ratio) of each monomer: ¹³ C-NMR (400 MHz, temperature: room temperature, solvent: deuterated chloroform).
(2) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn): measured under the conditions of gel permeation chromatography (GPC); temperature: normal temperature, solvent: chloroform did.
(3) Glass transition temperature (Tg): obtained from an endothermic peak when the temperature was raised from room temperature to 260 ° C. using a differential scanning calorimeter (model EXSTAR600, DSC6200) manufactured by Seiko Denshi Kogyo Co., Ltd.
(4) Total light transmittance, Δ (delta) Y (yellowness): 30 mm × 30 mm × 3 mm press molded body, Suga Test Instruments Co., Ltd. Haze Meter (HGM-2K) and Color Tester (SM-7) ).
(5) Refractive index: Using an Abbe refractometer (model: 2T) manufactured by Atago Co., Ltd., using a light source with a wavelength of 589 nm, aligning the reference with a standard sample made of glass having a refractive index of 1.5162. It was measured. The press-molded body was produced using a compression molding machine (model: NF-37) manufactured by Shindo Metal Industry Co., Ltd.

<Comparative Example 1> Copolymer of ethylene and phenyl norbornene In an ethylene atmosphere, toluene and phenyl norbornene-toluene solution were added to a 1.6 l autoclave so that the phenyl norbornene concentration was 20 mol / l and the total liquid volume was 640 ml. I put it in. Methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) was added 5.88 mmol based on Al, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1.5 μmol, ethylene was introduced and pressure was added. Was maintained at 0.2 MPa for 60 minutes at 80 ° C.

  After completion of the reaction, ethylene was depressurized while allowing to cool, and the system was replaced with nitrogen. Thereafter, 3.0 g of silica (made by Fuji Silysia Co., grade: G-3 particle size: 50 μm) with the adsorbed water content adjusted to 10 wt% was added and reacted for 1 hour. The reaction solution was placed in a pressure filter (Advantech Toyo Co., Ltd., model KST-90-UH) set with filter paper (5C, 90 mm) and Celite (Wako Pure Chemical Industries, Ltd.), and pressure filtered with nitrogen for polymerization. The liquid was collected. The polymerization solution was dropped little by little in 5 times amount of acetone to precipitate a produced polymer. The precipitated polymer was dissolved again in toluene, and once again added dropwise in 5 times amount of acetone to reprecipitate the polymer. The obtained polymer was dried at 100 ° C. under vacuum, and it was confirmed by GC measurement after drying that no unreacted monomer remained in the polymer.

  The yield of the polymer was 44.1 g, Mw = 142,000, Mw / Mn = 1.74, and the polymerization activity was 322 kg-polymer / g-Zr · h. The molar ratio of ethylene to phenyl norbornene contained in the polymer was ethylene: phenyl norbornene = 56: 44, and the glass transition temperature was 144 ° C.

<Comparative Example 2> Copolymer of ethylene and indanyl norbornene The same procedure as in Comparative Example 1 was conducted except that the monomer was changed to indanyl norbornene and the monomer concentration was changed to 1.0 mol / l. The copolymer yield was 27.0 g, Mw = 159,500, and Mw / Mn = 1.93. The polymerization activity was 789 kg-polymer / g-Zr · h, the molar ratio of ethylene and indanylnorbornene contained in the copolymer was ethylene: indanylnorbornene = 63: 37, and the glass transition temperature was 158 ° C. there were.

<Comparative Example 3> Copolymer of ethylene and norbornene In an ethylene atmosphere, toluene and a norbornene-toluene solution were placed in an autoclave having a capacity of 800 ml so that the norbornene concentration was 2.86 mol / l and the total liquid volume was 411 ml. 1.18 mmol of methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) on the basis of Al, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride (0.3 μmol) were added, ethylene was introduced and pressure was added Was kept at 0.2 MPa for 30 minutes at 80 ° C. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The polymer yield was 41.4 g, Mw = 207,500, Mw / Mn = 1.69, and the polymerization activity was 3025 kg-polymer / g-Zr · h. The molar ratio of ethylene and norbornene contained in the polymer was ethylene: norbornene = 44: 56, and the glass transition temperature was 145 ° C.

<Comparative Example 4> Copolymer of ethylene and norbornene mixed with hydrogen Comparative Example 3 except that a mixed gas in which ethylene was mixed with hydrogen was used in place of ethylene so that the molar ratio was hydrogen / ethylene = 0.00086 Polymerization was carried out under the same conditions as in. The yield of the polymer was 23.3 g, Mw = 127,500, Mw / Mn = 1.6, and the polymerization activity was 1703 kg-polymer / g-Zr · h. The molar ratio of ethylene and norbornene contained in the polymer was ethylene: norbornene = 46: 54, and the glass transition temperature was 149 ° C.

<Example 1> Copolymer of ethylene and methylphenylnorbornene Under an ethylene atmosphere, toluene and methylphenylnorbornene were added to an autoclave having a capacity of 200 ml with a methylphenylnorbornene concentration of 0.98 mol / l and a total liquid volume of 50 ml. I put it in. Methylaluminoxane (manufactured by Albemarle, MAO 20 %% toluene solution) was added with 2.0 mmol of Al standard, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 0.5 μmol, and ethylene was introduced. While maintaining the pressure at 0.1 MPa, the reaction was carried out at 80 ° C. for 30 minutes. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The yield of the polymer was 5.32 g, Mw = 14,000, Mw / Mn = 1.87, and the polymerization activity was 233 kg-polymer / g-Zr · h. The molar ratio of ethylene and norbornene contained in the polymer was ethylene: methylphenylnorbornene = 60: 40, and the glass transition temperature was 145 ° C.

  <Example 2> Methylphenylnorbornene copolymer: Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride used as a catalyst In an ethylene atmosphere, a methylphenylnorbornene concentration of 2.0 mol / in an autoclave having a capacity of 800 ml l, toluene and methylphenylnorbornene were added so that the total liquid volume was 320 ml. Methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) was added 5.88 mmol based on Al, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1.5 μmol, ethylene was introduced and pressure was added. Was kept at 0.2 MPa for 15 minutes at 80 ° C. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The yield of the polymer was 34.43 g, and the polymerization activity was 1007 kg-polymer / g-Zr · h. Moreover, the glass transition temperature of the obtained polymer was 190 degreeC.

<Comparative Example 5> Methylphenylnorbornene copolymer: ethylenebisindenylzirconium dichloride is used as a catalyst. In an ethylene atmosphere, the methylphenylnorbornene concentration is 2.0 mol / l and the total liquid volume is 320 ml in an autoclave having a capacity of 800 ml. Thus, toluene and methylphenylnorbornene were added. Methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) was added at 16.17 mmol and 4.0 μmol of ethylenebisindenylzirconium dichloride based on Al, and ethylene was introduced to keep the pressure at 0.2 MPa while maintaining the pressure at 80 ° C. For 35 minutes. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The yield of the polymer was 16.72 g, and the polymerization activity was 79 kg-polymer / g-Zr · h. Moreover, the glass transition temperature of the obtained polymer was 135 degreeC.

<Comparative Example 6> Copolymer of methylphenylnorbornene: isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride is used as a catalyst. In an ethylene atmosphere, a methylphenylnorbornene concentration is 2.0 mol / l in an autoclave having a capacity of 800 ml. Toluene and methylphenylnorbornene were added so that the total liquid volume was 295 ml. Methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) was added 11.76 mmol based on Al, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride 3.0 μmol, ethylene was introduced, and the pressure was 0.2 MPa. The mixture was reacted at 80 ° C. for 60 minutes. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The yield of the polymer was 2.87 g, and the polymerization activity was 10 kg-polymer / g-Zr · h. The resulting polymer had a glass transition temperature of 155 ° C.

Table 1 shows the polymerization activity and glass transition temperature of the copolymers obtained in Example 2, Comparative Example 5 and Comparative Example 6.

  As can be seen from the results of Table 1, when an aromatic-containing norbornene is copolymerized in the presence of a metallocene catalyst using methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, a general metallocene is used. Compared to ethylenebisindenylzirconium dichloride and isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, which are catalysts, it is found to be very highly active and have higher copolymerizability. It was.

<Example 3> Evaluation of heat resistance Table 2 shows the comonomer ratio and glass transition temperature of the polymers obtained in Comparative Examples 1 to 3 and Example 1.

Table 2 shows the comonomer ratio and glass transition temperature of the polymers obtained in Comparative Examples 1 to 3 and Example 1.

  From Table 2, the methylphenyl norbornene copolymer obtained in Example 1 has a lower comonomer content than the norbornene-free norbornene copolymer obtained in Comparative Example 3, but has a comparable glass content. It has a transition temperature. Furthermore, even when compared with the phenyl norbornene copolymer and indanyl norbornene copolymer obtained from Comparative Examples 1 and 2 having similar substituents, they have the same glass transition temperature with a small comonomer content. Yes.

<Example 3> Evaluation of oxidation resistance The polymers obtained in Comparative Examples 1 to 3 and Example 1 were analyzed with a differential scanning calorimeter (DSC). The DSC measurement was performed by raising the temperature from 30 ° C. to 350 ° C. at a temperature raising rate of 5 ° C./min in the air (air supply flow rate 50 ml / min). The results are shown in FIG. 1, and the heat generation start temperature is shown in Table 3.

  From FIG. 1, in the copolymer using a comonomer having hydrogen at the benzyl position such as phenyl norbornene and indanyl norbornene, an exothermic peak due to an oxidation reaction appeared from around 140 to 150 ° C. exceeding the glass transition temperature. On the other hand, the methylphenylnorbornene system had no exothermic peak up to around 220 ° C., and it was confirmed that it became difficult to oxidize to higher temperatures by replacing the hydrogen at the benzyl position with a methyl group. In addition, it was confirmed that the oxidation resistance was equal to or higher than that of the norbornene-based heat generating near 200 ° C.

<Example 4> Evaluation of crosslinking reaction inhibitory effect and optical property evaluation The polymers obtained in Comparative Examples 1 to 3 and Example 1 were each press-molded at a temperature of 180 ° C. Table 4 shows the state of gel generation when the press-molded product was dissolved in methylene chloride, and Table 5 shows the GPC measurement results of the solvent-soluble components. In addition, Table 6 shows the results of measuring optical characteristics using the molded body.

  As shown in Table 4, it was confirmed that the occurrence of gel during press molding was suppressed by replacing the hydrogen at the benzyl position with a methyl group, and no increase in molecular weight due to the crosslinking reaction occurred.

  As shown in Table 6, by replacing the hydrogen at the benzyl position with a methyl group, the decrease in optical properties during press molding is suppressed, while maintaining transparency equal to or higher than that of a norbornene system that is less prone to deterioration, and higher It was confirmed to have a refractive index.

  The results of synthesis and evaluation of copolymers of ethylene, norbornene, and aromatic-containing norbornene are shown below.

<Comparative Example 7> Ethylene, norbornene, and phenylnorbornene copolymer Under an ethylene atmosphere, 0.77 mol of norbornene and 0.13 mol of phenylnorbornene were added to an autoclave having a capacity of 800 ml, and toluene was added so that the total liquid volume became 320 ml. (Total monomer concentration: 2.82 mol / l). Methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) was added 3.91 mmol based on Al, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1.0 μmol, ethylene was introduced and pressure was added Was kept at 0.2 MPa for 20 minutes at 80 ° C. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The yield of the polymer was 28.52 g, Mw = 183,000, Mw / Mn = 1.91, and the polymerization activity was 947 kg-polymer / g-Zr · h. The molar ratio of ethylene, norbornene, and phenylnorbornene contained in the polymer was ethylene: norbornene: phenylnorbornene = 48: 46: 6, and the glass transition temperature of the polymer was 150 ° C.

<Example 5> Ethylene, norbornene, and methylphenylnorbornene copolymer Under an ethylene atmosphere, 0.24 mol of norbornene and 0.023 mol of methylphenylnorbornene are added to an autoclave having a capacity of 200 ml so that the total liquid volume becomes 95 ml. Toluene was added (total monomer concentration: 2.78 mol / l). 1.29 mmol of methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) and 1.33 mmol of methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride (0.33 μmol) were added based on Al, ethylene was introduced, and pressure Was kept at 0.2 Mpa for 60 minutes at 80 ° C. Subsequent operations were performed in the same manner as in Comparative Example 1.

  The yield of the polymer was 5.55 g, Mw = 153,500, Mw / Mn = 1.66, and the polymerization activity was 1106 kg-polymer / g-Zr · h. The molar ratio of ethylene, norbornene and methylphenylnorbornene contained in the polymer was ethylene: norbornene: methylphenylnorbornene = 47: 49: 4, and the glass transition temperature of the polymer was 168 ° C.

<Example 6> Evaluation of heat resistance of ternary copolymer Table 7 shows a copolymer using two types of monomers (Comparative Example 3 and Example 1) and a copolymer using three types of monomers (Comparative Example). 7 and Example 9) are shown for each monomer content and glass transition temperature.

As can be seen from Table 7, it was found that higher heat resistance can be obtained by using a small amount of cyclic olefin by combining three kinds of monomers.
These copolymers were press molded and analyzed for GPC and optical properties. Table 8 shows the GPC results.

  Copolymers using phenylnorbornene as a comonomer have increased molecular weight and molecular weight distribution due to a cross-linking reaction, whereas copolymers using methylphenylnorbornene as a comonomer change both in molecular weight and molecular weight distribution. It was revealed that no cross-linking reaction occurred.

Further, from Table 9, it was found that the ethylene-norbornene-phenylnorbornene copolymer has a higher refractive index than the ethylene-norbornene copolymer, but the total light transmittance and ΔY are lowered. In contrast, the ethylene-norbornene-methylphenylnorbornene copolymer was found to have the same refractive index, total light transmittance, and ΔY.
From these results, it was found that the ethylene-norbornene-methylphenyl norbornene copolymer has higher heat resistance with a small amount of cyclic olefin used, improved heat aging resistance, and maintains excellent optical properties.

  According to the present invention, it has excellent polymerization activity, improved heat aging resistance, heat resistance and optical properties necessary for use as an optical material for aromatic-containing norbornene copolymers, and has a high glass transition point at the same time. Provided is an efficient process for producing aromatic-containing rubornene copolymers using satisfactory catalysts.

The result of having performed the differential scanning calorimetry about each polymer obtained by Comparative Examples 1-3 and Example 1 is shown.

Claims (5)

An α-olefin and an aromatic-containing cyclic olefin composed of 5-methyl or ethyl-5-phenyl-bicyclo [2,2,1] hept-2-ene are mixed with methylene (cyclopentadienyl) (tetramethylcyclopenta A method for producing an aromatic-containing cyclic olefin copolymer, comprising copolymerizing in the presence of a catalyst containing ( dienyl) zirconium dichloride and methylaluminoxane. Said α- olefin, and the aromatic-containing cycloolefin, further, bicyclo [2,2,1] hept-2-ene aroma of claim 1 and a cyclic olefin comprising a (norbornene) Ru by copolymerizing For producing a group-containing cyclic olefin copolymer . 3. A differential scanning calorimeter obtained by the production method according to claim 1 or 2 (in air at a temperature rising rate of 5 ° C./min and a temperature of 30 ° C. to 350 ° C. and an air supply rate of 50 ml / min) An aromatic-containing cyclic olefin copolymer having an exothermic starting temperature of 180 ° C. or higher. Including optical science material an aromatic-containing cycloolefin copolymer according to claim 3. Including electrical and electronic materials an aromatic-containing cycloolefin copolymer according to claim 3.

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